The present invention relates to a new thin film deposition method and a new deposition apparatus that employs a heated coiled filament and multiple gas inlets. At least one inlet directs at least one type of suitable reactant gas, or gases, into a gas confinement cup contained with a chamber such that the gases pass through the heated coiled filament. The method of the present invention is used to deposit advanced thin films at both a high quality and at high deposition rate. Hot-filament process is used to deposit semiconductor materials with improved materials properties onto desired substrates.
The present invention was made under research grants from the National Renewable Energy Laboratory/US Department of Energy, under Contract or Grant No(s). ZAF-8-17619-14, ADD-8-18669-08, and NDJ-2-30630-08 who may have certain rights thereto.
Thin film semi-conductors are useful in a variety of electronic devices such as solar panels, liquid crystal displays and other related technologies. One method for making these thin semi-conductors, such as amorphous silicon or microcrystalline silicon, is to deposit a thin film onto a suitable substrate using a chemical vapor deposition (CVD) process. The most commonly used CVD method to deposit amorphous or microcrystalline silicon is plasma enhanced chemical vapor deposition (PECVD). However, such a PECVD method leads to low rate of film deposition.
An alternative chemical vapor deposition process that leads to a higher deposition rate is a hot-wire chemical vapor deposition (HW CVD) process which uses a thin foil or small metal diameter wire filament as the hot-element of the process. The element, which can comprise tungsten, tantalum or molybdenum, for example, is heated to a high temperature and a gas is caused to flow over or into contact with the hot filament. The hot filament breaks down the gas into its constituents. These constituents then are deposited on an adjacent substrate.
However, there are many drawbacks associated with these conventional hot-wire chemical vapor deposition processes. Several groups have studied the use of hot-wire CVD process to deposit advanced thin films such as amorphous silicon based films. Mahan et al. (U.S. Pat. Nos. 5,397,737, 5,776,819), Iwancizko et al. (U.S. Pat. No. 6,251,183), Madan et al. (U.S. Pat. No. 6,214,706), and Molenbroek et al. (U.S. Pat. No. 6,124,186) deposited films using a hot-wire process that employs a wire spanning within the chamber to dissociate gases introduced into the chamber. However, the rate of deposition for this method is typically less than 50 A/sec. In addition, due to the lack of high controllability of the concentration of radicals, these methods have failed to produce amorphous silicon based solar cells with efficiency comparable to state-of-the-art solar cells produced using PECVD method.
Ichikawa, M., Takeshita, J., Yamada, A, and Kongai, M., Jpn J. Appl. Phys. 38, L24 (1999) used a coiled hot-filament near the gas inlet to deposit polycrystalline silicon and microcrystalline silicon materials. Although such a filament design could, in theory, lead to a higher deposition rate, it has failed to be used to produce photovoltaic devices with reasonable efficiency. This is again due to the lack of sufficient control of the concentrations of reactive species in the reactor. For example, during the deposition of amorphous silicon, there are significant amounts of the Si, SiH, and SiH2 species in the mixture, while the species responsible for high-quality film is believed to be the SiH3 species.
Yu, S., Gulari, E., and Kanicki, J., Appl. Phys. Lett., 68, 2681 (1996) used a filament spanning inside the chamber plus a gas dispersal ring closer to the substrate to deposit large-grain size polycrystalline silicon for application in flat panel displays. However, high quality film suitable for flat panel display device application or photovoltaic application could not be demonstrated using this method. As indicated above, all of these methods do not allow practioners to achieve high controllability of the concentration of radicals, and, therefore are difficult to use to produce high quality thin film materials such as amorphous silicon based materials for high-efficiency photovoltaic applications. Further, the rates of deposition that are achieved using HW CVD with span filaments inside the chamber are not sufficiently acceptable, and therefore, add to the cost of manufacturing useful products.
Therefore, there is needed in the art of hot-wire chemical vapor deposition processes a method and an apparatus which provide improved deposition results and at an increased deposition rate.
There is a further need to provide a method and an apparatus to increase the efficiency of deposition of a desired element onto a substrate.
There is a further need for an apparatus which avoids contamination during the deposition process.
Further, there is a need for a commercially practical hot-wire chemical vapor deposition process which is reliable in a manufacturing setting.
It is also desirable to have an improved method to produce amorphous silicon and microcrystalline silicon products having improved properties.
This invention relates generally to apparatus and method for hot-filament chemical vapor deposition of thin film material onto a substrate, and more particularly, to a novel apparatus and method for depositing advanced thin films and coatings for use in a broad range of applications including photovoltaic devices, thin film transistors, ac color plasma display panels and hard coatings for tools.
Until the present invention, no one had thought to combine the advantages of using hot-wire coil filament and using multiple gas inlets to produce high quality semi conductors. The hot-wire coil filament is employed to achieve a most-efficient excitation and/or disassociation of the gas. The gas is directed into the reactor near the coiled filament, thus, achieving a high deposition rate. According to the present invention, at least one suitable reactant gas is directed into the reactor through inlets near the substrates (and not near the filament). This gas can be remotely (i.e., not directly) excited by the gas species which are introduced from inlets near the filament. Such a combination allows for maximum control of reactive species inside the deposition chamber. This method is useful to deposit various films with desirable optoelectronic and mechanical properties that are ideal for use in a broad range of devices.
According to certain methods of the present invention, a-Si thin films are deposited at a rate at least about 400 to at least about 800 A/sec, which is a factor of 100 to 200 times faster than currently used processes.
The hot-wire deposition system of the present invention includes an apparatus for and a method for a hot filament chemical vapor deposition process. The apparatus includes at least one coiled hot filament in a chemical vapor deposition (CVD) chamber. Such a system is useful for the fabrication of high efficiency amorphous silicon based solar cells at a high rate. The hot-wire CVD process is especially useful for the deposition of 1) high quality a-Si (amorphous silicon), and a-SiGe (amorphous silicon germanium) materials at high deposition rates, 2) high quality poly-Si (polycrystalline silicon) and xcexcc-Si (microcrystalline silicon) films for the narrow bandgap absorber layer, and 3) high-quality diamond-like carbon coatings.
In one aspect, the present invention relates to a method for the deposition of a thin film material on a substrate which includes:
providing a deposition chamber and a substrate in the deposition chamber,
applying a vacuum for evacuating the deposition chamber to a sub-atmospheric pressure,
heating a dense hot filament to about 1500 C. or higher,
introducing at least one first reactant gas into at least one first gas inlet, the first gas inlet being adjacent the dense filament, and
introducing at least one second gas into at least one second gas inlet, the at least one second gas inlet being in a spaced apart relationship to the dense filament, and, in certain embodiments, adjacent the substrate.
In another aspect, the method can include at least one further step of heating the substrate to a temperature between about room temperature and about 500 C. or higher to enhance the surface mobility of atoms during film growth In yet another aspect, the invention includes the further step of evacuating the deposition chamber to a sub-atmospheric pressure. In certain embodiments the chamber can be evacuated to a pressure of about 10xe2x88x925 Torr or less.
According to certain preferred aspects of the present invention, the dense hot filament can be a densely pack filament coil or other dense filament structure such as, for example, tungsten, tantalum or molybdenum. The suitable reactant gas, or gases, introduced into the evacuation chamber can be one or more of the following: H2, silicon hydrides (SiH4, Si2H6, Si3H8, SixH(2x+2)), silicon fluorides, germanium hydride, germanium fluoride, carbon hydride, carbon fluoride, and the like.
While the embodiments of this invention have been described relating to the use of silane gases, the spirit and scope of the invention is not to be limited to these specific gases. Rather, the list of gases herein is meant as a guide and the invention is not to be limited to these gas precursors but could include other suitable precursors and other combinations as are apparent to those of skill in this art.
In yet another aspect, at least one electrode can be included in the deposition chamber to strike and maintain a plasma for the film deposition. The electrode preferably delivers power at the frequency of 0 (DC) to 150 MHz (VHF) including 13.56 MHz (RF). The plasma can be stricken during the interface treatment, or during simultaneous plasma and hot-filament deposition.
Using the method of the present invention, deposition rates up to at least about 800 A/sec are achieved. In certain embodiments of the present invention, the thin film material is deposited at a rate substantially higher than that of PECVD. Also, in certain embodiments, the deposition rates range from at least about 150 A/sec to about 800 A/sec, and in certain other embodiments, the deposition rates range from about 400 to about 800 A/sec.
The present invention also relates to an apparatus for the deposition of thin film material upon a substrate. The apparatus includes a deposition chamber, a vacuum source for evacuating the deposition chamber to sub-atmospheric pressure, a dense hot filament capable of being heated to 1500 C or higher, at least one first gas inlet adjacent the dense filament for introducing at least one gas into the evacuated deposition chamber through the first inlet, and at least one second gas inlet in spaced apart relationship from the dense filament for introducing at least one gas into the evacuated deposition chamber through the second inlet. The apparatus can include a means for heating the substrate to a temperature between room temperature and 500 C. or higher to enhance the surface mobility of atoms during film growth. The deposition chamber is capable of being evacuated to a pressure of about 10xe2x88x925 Torr or less. In certain embodiments, the dense hot filament comprises a densely pack filament coil or other dense filament structure.
The apparatus can further include at least one electrode in the deposition chamber to strike and maintain a plasma for the film deposition. The electrode preferably delivers power at the frequency of 0 (DC) to 150 MHz (VHF) including 13.56 MHz (RF). The plasma can be stricken during the interface treatment or during simultaneous plasma and hot-filament deposition.
The material made using the apparatus and method of the present invention is useful as an active layer in a photovoltaic material, in a thin film transistor, in an ac color plasma display, and as a hard coating for tools.